Mica products with inorganic binders



106. COMPOSITIONS, Examiner COATING Rv PLASTIC. 7% Patented Oct. 2, 1934 Dress deters-nus ,..moa' Pnonncrs wn'n mondamc "1. .LJBINDERS I I' A. Bought on, 0ambridge,'Mass., assignor e I to New England Mica 00., Waltham, Mass, a corporation of Massachusetts it No Drawing. Application-Marcia 1931, Serial N0. 521,378 .19 claims. "(ci ia-2.6)

ei invention relates to built-up flexible inwholly inorganic nature, do not burn or char, and

organic bound mica products, made from lates, arev highly resistant to the action of oils and or flakes, or films of mica cemented toRETeT'B! organic solvents. V amc wear, an w c o ay e 8111 aly j'This group of substances includes those anoma- 5 shaped into plates, tube or other special products lous inorganic compounds which are capable of during the processor manufacture. forming highly viscous aqueous solutions in the An object of the invention is to provide a flexible presence of a moderate amount of water, holding high-resistance fire-proof and non-combustible a part or all of this water in colloidal combina- 3 mica product, which may be manufactured in any tjon or otherwise considerably more .flrmly than desired shape, and of any desired thickness. is ordinarily the case with water of solution. Ihus 55 A further object is to provide mica products when such viscousaqueous solutions .are heated, which increase in resistance with age. and which they as a rule evolve this water slowly above 100? possess still higher resistance after having been (3., forming fluids of increasingly greater'viscosity;

l heated to higher than the temperatures to which and if the heating iscontinued a part of the dissaid products are normally submitted. solved substance may finally precipitate or the Aa-further object is to provide-flexible mica product may be ome substantially anhydrous, products which are free from organic materials, forming a, g1ass 1nde ed,':a.11 0113118 substances and that will not carbonize or disintegrate after known to' me tub in this classification, when l prol n ed xcessiv h atin 1 strongly jheated even though then solid, melt to v Afurther objectistoprovideflexible-mica prodf m vi u ji jd whi h after cooling have 5 acts which are not affected by organic solvents arkedlyglass-like properties,,or'are true glasses. h as Oils, n which m y e used in circu- Qf'The 'propertybf formin' lasses on fusion and lating oil cooled appara us, r with th r pp subse uent coolin owever,is no .00 i H o s mill p n w i h Oil may be brought in c n mmfiorganic substances, and is not Without r r -1 cited asan exclusive property .ofithem. .On"the Q9 A further object is to prepare flexible mica products which will have a definite temperature other hand, the property of yielding u 'water of solution slowl and at super-rr'mal temperatures, Z IE5 case above TUE C. to I55 CJrs' given range of flexibility, the degree of whichmay be m pre-determined, and in which there is not :any slippage or buckling of the mica flakes;

, A further object is to provide an inorganic bound mica product whichis flexible and possesses a'high dielectric strength at one temperature, and is less flexible or is inflexible and possessing a higher dielectric "strength ,at a higher tems Derature. I r5 f Other objects of the invention'will be :apparent to those skilled in the 'art after reading the specification. .40 The flexible mica products of'commerce'heretofore available have been bound with a'resin usually containing a flexibilizing medium such as castor oil. Such an organic-boundproducthas obvious disadvantages; :ior exampla-it .is :disintegrated rapidly in the presence of .oils or organic solvents; and when over-heated itchars and may actually burn, constituting agenuine fire risk. i i (4'. "r-"l-vrizrtiy rr-si After considerable research with mica products made with many types of binders,--1 have dis covered that a highly limited group ofrinorganic substances, all of similar-physical properties for the present purposes, may be used as inorganic binders in the production ofa new kind of flexible mica product, which binders, zhecause nf their as .the fundamentally important characteristic of the group of substances herein-cited, and is to the best of my knowledge limited tothem i Exf samples of such substances are:-

me he masses; 81, 511 s ance g ass w en prepargd by fusing and cooling Prima y sodium phosphate; I,

(2) Ammonium meta hos hate r (-3) fietaphospfionc acid e irdinaryglacial phosphoric acid of commerce);

(4:) Sodium metaborate sodium mono re 111. a 'r'" 5)- prdinary sodium silicate,-or waterlass." whammtures above about 80 C. should be considered vas super-normahwbecause of the ;high wiscosity or is "TR-ff 0W; e terak wn' as solutions of this substance which are stable at this temperature. aHeating to G. produces in the watereglassesan intumescence', -,due to the fail-- ure of steam bubbles which are formed to escape from the highly viscous liquid, and so by expan= sion destroys the unusual :binding properties which sodium silicate is known to have. '?Never-j theless, even when a mass of intume'sced sodium silicate which isxstable at, say,; 105 C. is subjected to high pressureitcoalescesandtorms a glass-like material that is; adhesiveito mica: and will'bond mica pieces into a more or less flexible sheet at such temperatures. Sodium silicate may, therefore, also be considered a typical example.

While reference has been made herein to the substances, sodium metaphosphate, ammonium metaphosphate; metaphosphoric acid, sodium metaborate, and sodium silicate, it will be apparent that other chemical substances having like properties could be used which are capable a forming viscous liquids, when associated with limited amounts of water, and holding that water at super-normal temperatures more tenaciously than ordinary water of solution is held, evolving it only slowly at higher temperatures, without great precipitation of crystalline solids if any, and without the loss of the property of high viscosity; a few border line compounds develop some dispersed flne crystal grains, but such mixtures alsofunc tion well as binders for mica flakes. Also a variety of salts of the element beryllium may be prepared in the adhesive gummy state, and function is binders for flexible mica products. For example, an aqueous solution of sodium beryllium sulfate forms by evaporation a thick viscous syrup; and the basic sulfates of beryllium form gummy masses, fiimilarly, certain salts of the element vanadium also form viscous solutions of the same general physical properties; examples of these are the double salts with the phosphates. Many other specific examples will be known to those fa ar with the physical properties of such :1. Th binder "Tor binding mica pieces together to form a commericallyuseful inorganic bound flexible sheet, I use an aqueous solution of, or combination with, metaphosphate or-other members -'of the limited class of inorganic substances having the characteristic properties described above.

fflodium'metaphosphate (1) itself is easily pre- I we er sou e orm by'fusion or the primary sodium orthophosphate, or ammonlurh -"orthophosphate of '-commerce. The compound used is theglass like hexametaphosphate, the so-called Graharns salt, and with of water bolls at approximately 105 C. tel-106 G.- The approximately anhydrous melt is allowed to oooland forms a colorless, transparent, very hard glass. It is crush'ed'and powdered to pass a '100 mesh screen, and equal parts of this material and either cold or warm water are rapidly and thoroughly mixed. The mixture, at'flra 'mudslike, quickly becomes highly viscous with evolution of considerable heat, and isthen ready to be applied to 'bhe'mica pieces .(sometimes called mica films, splittings, rtragments,

flakes, etc).

-:.Ammonium metaphosphate 1(2) is prepared from pr n. rm phosphatejutin this the decomposition of the latter salt takes place at lower temperatures, and it is sumeient to heat the primaryiorthobhosphateuntil it melts and the liquid boils. isrcontinued until the temp rature --r.eaches the vicinity of 8fl0-.C.-when the liquid is allowed to cool. At rdinary t mp ratures-it then resembl ph l in and is. a cl ar c lorless'and classlike pr duct, and may b use we b n o mice flake un su fi n fl di is-ebteined to permit a l cat o l u d hi1!" brush or spray; c it m y-"b mixed w th enough water to give a solution thatean be ap ied a ord nar temperature, in u dehy rat on Mat s. nflected a heated table, or in some other convenient way.

Meta hosphoric acid (3), that is, glacial phosmam dissolved in an excess of water and the excess removed by boiling, or it may be crushed and powdered topass a 100 mesh screen, and thereafter treated as described above under sodium metaphosphate.

Sodium metaborate (4), is an article of com- 1s a so a viscous solution of it prepared in the usual way by dissolving in water and boiling until enough water has been driven oil to leave an association of water and inorganic salt having a desired degree of viscosity. 'Ihe'solution thusobtained is used to bind the mica flakes as described above. Sodium metaborate solution containing about of water boils at'appro'ximately 106 C. to 107 C.

' Sodium silicate (5), is the ordinary water-glass o commerce. e solution is applied to the mica flakes as above described, and upon careful drying and rolling on a hot table produces a flexible mica plate; this is a new and novel use for water-glass in the binding of mica flakes, in that a new product, a flexible mica sheet, is obtained; heretofore, all water-glass-bound mica products have been by intent and design hard and rigid fi One of the important commercial advantages resulting :from the use of this class of inorganic binders for flexible mica products is that by yarying the amount of water associated with and retained in the'inorganic compound binder-the temperature range may be varied over 'which the mica product thus produced has a desired degree of flexibility. Thus, for use at normal temperatures and with sodium metaphosphate, a mixture of equal parts of the compound "and water is used as the binder, producing with moderate fur-.- ther dehydration a product 0! good flexibility and without slippage oi the mica pieces over one another under pressure, and without buckling. such a binder then containing %+40% .of water. However, by lowering the amount of water to 25% to 80% cries of the total, a product may be prepared which is too stifl for use at ordinary temperatures, but is of :useful flexibility at a temperature'range in the vicinity of 50 (En-Similarly. M much as -40%-,-45% of water he in association with-the sodium metaphosphate a mica product is obtained that is-too flexible for use at ordinary temperatures and shows slippage, but without dehydration is o us flfl fl xibility and without slippas 'at, say. Zero degrees C.- n these properties, therefore, the inorganic-bound flexible mica product herein described resembles the common organic-bound flexible mica product of However, wh n de dration is carrie tu ther by h at a hard non-flexible plate of enhanced dielectric strength is th bind 2 g0%-2 5%- or less of water." 7 n th pr wa i u n ic fl xi mi a P duc -smith t in r an binde s herein dei d here v n a e is ak o h D c sr a p p rt o metaphosphate and some of the other substances he n de b d. w eb a gro mless gummy-like adhesive-fluid is formed-lay the association of the solid with a amount of water, th being defini e i ea range of viscosity to practically a at ordinary temperatures. as o iati n may b b oug t about byu) mix-ins of solid with water. or (3 bynsol t en in an exc ss oi wat wit subsequen emanation of the e cess-or 1 i ilo COMPOSITIONS, COATING OR PLASTIC.

aurzaovs any other convenient andpracticable manner such asby boiling a dilute solution :until only the desired amount of water is left, as indicated by the boiling temperature. 1

, The process ---ln making flexible mica productsiwith this kind of inorganic hinder, the mica pieces are laid as usual on a wire frame or other suitable supporting surface, the binder applied by brushing, spattering, spraying, or in any other con-' venient way, another layer of mica pieces added and more binder applied, 'and this process repeated until a sheet of somewhat greater than the desired flnal thickness is produced, ending with a covering of mica pieces. The sheet or other products, now a flrmly adhering unit, is transferred to a hottable and rolled, or, with irregularly shaped products pressed, until any air bubbles are removed and the desired thickness obtained. It is then set aside to cool and is thereafter ready'for storage or shipment. The process of manufacture does not "require ovenbaking, solvent recovery, nor press heating; it is sanitary and rapid, and there is no 'flre risk.

The product and properties The flexible sheet or product thus prepared shows the commercially useful flexibility over the temperature range for which it is intended to be used. It is transparent and colorless, or approximately so unless artificially colored, '(as by the addition of a water-soluble dye or a colored salt such as a chromate, or the treatment-of the binder compound with a color-producing inorganic substance such, for example, as a cobalt salt, by which means products bearing designs, or variegated or mottled appearing products may be made, or suitable trade-mark characters may be developed within the product). It shows no slippage and no buckling. It is non-combustible and non-inflammable, and does not support combustion. It is unaffected by oils, waxes, and almost all common organic solvents. Thin sheets may be formed into tubes of any desired thickness of wall by rolling and cementing with additional binder, and these may then, if desired, be hardened to rigidity by simple dehydration.

when the product is subjected to gentle heat, it gradually loses water, becoming progressively stiffer until a point of equilibrium is reached between the contained water and the temperature. With increasing temperature the product becomes less flexible, but it acquires an increased dielectric strength, and is mechanically stronger.

In the case of a plate bound with certain compounds of this type, such as sodium metaphosphate, the binder eventually may crystallize somewhat, but the plate does not even then fall apart unless subjected to tearing and distortion. Tubes made of such a plate retain their tubular form even when highly opacifled by drying out. In this opaque dried out condition, however, the product is even a better electrical resister than when first prepared, the dielectric strength then running upwards of 300 volts per mil puncture resistance. When subjected to still higher temperatures (300 C.-500 C.) the dried-out opaque binder again melts and under pressure forms a highly adhesive mica binder of still greater enhanced electrical resistance. In this respect such a plate shows a vast improvement over the organic bound plates heretofore available, which, as is well-known, show diminishing electrical resistance as the temperature rises.

ma Mwmcmmuzwmnyiiw.M Les sPlates bound with other materials such as am-. monium metaphosphate, on-the other hand do not ordinarily opacify rand crystallize, but the binder retains its viscous glassy condition to the temperature of decomposition. Wlth'sodium 'metaborate used as binder material, a :product of somewhat greater dielectric strength :is produced, having initially about 400 volts per mil, 'andafter being dried out under the action of heat, about 900 volts per mil. The product in other respects is quite similar to though not identical with, a product bound with sodium metaphosphate :binder. 3. 'With water glass as a binder material, a different class of products is obtained. .A mica prodnot bound with this material may be used only below about C., for above this temperature the water-glass (sodium silicate) solution, as is well-known, becomes so viscous that its associated water has difliculty in escaping, tough-walled bubbles are formed and the phenomenonknown as intumescence takes place, resulting in separation of the mica pieces and loss of integration. Nevertheless, when the water-glass-bound flex ible mica product is heated under high pressure, integration is maintained, and the escaping water forces its way out without the destruction of the product. -The electrical resistance of the water-glass-bound productis low compared with that of the other binders described herein, and its usefulness is therefore limited to those purposes which do not require the customary high dielectric strength. However/the use of waterglass solution as a binder-for producing flexible mica products, for example sheets,tubes, etc., is entirely-successful and practical, 'and such jflexible mica products are a genuine novelty. Heretofore, when water-glass has been used as a binder, only hard stiff plates or other products were desired, and heretofore the attempt was made to use said products at temperatures above 80 C.; as a result the plates disintegrated and water-glass came into disrepute as a practical binder for cementing mica plates into a sheet or other product for any purpose whatever. r20 In addition to the use of individual salts or compounds of the class herein described as binders for flexible mica products, there may be used mixture of such salts as the binder; for exampe here may be used equal parts (on a dry 125 basis) of sodi sphate and sodium metaborate as the binder, in which case a solution of one salt may function as a solvent for another salt, and flexible mica products obtained by such a mixture have shown excellent properties; thus a flexible mica sheet with the above double salt binder possessed when dried out a dielectric strength of 846 volts per mil.

I claim:-

1. A flexible integrated mica product, consisting of built-up mica flakes, said mica flakes cemented and bound together by a viscous inorganic binder, said binder consisting of at least one selected from the group of the soluble viscous aqueous colloidal adhesive associations of metaphosphoric acid radicle compounds, metaborates, beryllium compounds, and vanadium compounds, the water in the binder of the mica product beingsufllcient to maintain said binder as a viscous colloidal adhesive.

2. A flexible integrated mica product, consisting of built-up mica flakes, said mica flakes cemented and bound together by a viscous inorganic binder, said binder consisting of at least one selected from the group of the soluble viscous 15 [.XHIIIIHBT 4 mzmze mucous coll da adhe e of ph p a i s' c m ounds.

beryllium compound an th w sin h i e thez ayro stbem sufficient to maintain said binder asa eelloidal adhesive, and the property ofrbeing flexible and high resistant-at one temperture, and less flexible, or inflexible, but of ,higher resistance after heating to a higher temperature andthencooling. :z 1 -41, 3. A flexible integratedmica product, eonsist ing of built-up mica flakes, said mica flakes ce-'- mented and bound together by a colloidal association of a viscous binder comprising a metaphosphate compound and water, the water in the binder of the mica product being sufficient to maintain said binder as a viscous colloidal adhesive. i 7 g 4. A flexible integrated mica product, consisting of built-up mica flakes, said mica flakes cemented and bound together by a colloidal association of a viscous binder comprising alkali metal metaphosphate and water, the water in the binder of the mica product being sumcient to maintain said binder as-a viscous colloidal adhesive. a a .I v 5. A flexible integrated mica product, consisting of built-up mica flakes, said mica flakes cemented-and bound together by acolloidal association of :a viscous binder comprising sodium metaphosphate and water, the water in the binder of the mica product being sumcient to maintain said binder as a-viscous colloidal adhesive w -6. A flexible integrated mica product consisting of built-up mica flakes, said mica flakes cemented and boi md together by a colloidal assogiaidonot a yiscous-bindercomprising metaphosphoric acidand water, the water in thebinder of the product being suificient to maintain said binder as a viscous colloidal adhesive.

7. A flexible integrated mica product, consist- 80 ing of built-up mica flakes, said mica flakes cementedsnd bound together bye colloidal association ot a .wiscous binder comprising sodium metaborate and water, the water in the binder of the mica-product being suflicient to maintain said 185 binder as a viscous colloidal adhesive. 1

method of makingflexible integrated mica products, which consists of cementing togethere plurality of mica flakes with an aqueous association of at least uu 2: ie binder selected from group oonsistingof visnous colloidal aqueous associations 5 ,metaphosphoric acid adicie compounds, m compounds, and vanadium compounds, rolling or pressing the assembled mass, and retaining sufficient water in the binder oi the completed mica product to maintain said binder viscons and the pnoduct flexible.

9. The method of making flexible integrated mica products, which consists of cementing together a plurality of mica flakes withan aqueous association of a plurality cfmutually dissolved adhesive inorganic binders selected irom the group consisting of viscous colloidal aqueous associations of metaphosphoric acid radicle compounds, metaborates, beryllium compounds, and :vanadium icompmmds rolling or pressing the assembled mass,-.and retaining suflicient water in the binder of the-completed mica product to maintain said binder viscous andthe product flexible. 110 

